TW201929311A - Metal-air flow secondary battery - Google Patents

Abstract

A metal-air flow secondary battery includes a discharge positive plate module, an air electrode module, a front case, a charge positive plate module, an intermediate case, a negative plate, and a back case. The discharge positive plate module and the air electrode module are disposed on a first side of the front case, and the charge positive plate module is disposed between a second side of the front case and the intermediate case. The negative plate is disposed between the intermediate case and the back case. Both of the front case and the intermediate case have a holding space for containing an electrolyte solution. The front case consists of a first electrolyte channel module and a second electrolyte channel module, wherein the first electrolyte channel module is disposed between the discharge positive plate module and the second electrolyte channel module.

Description

Metal air flow secondary battery

The present invention relates to a metal air battery, and more particularly to a metal air flow secondary battery.

Recently, metal-air secondary batteries having both charging and discharging functions have been gradually taken into consideration and developed. The cathode of a conventional metal-flow air secondary battery must have two kinds of catalysts, so that it can perform oxygen reduction reaction (ORR) during discharge, and reduce oxygen (O ₂ ) to hydroxide ions. (OH ^- ); or an oxygen evolution reaction (OER) during oxidation to oxidize hydroxide ions (OH ^- ) to oxygen (O ₂ ).

Since the electrolyte of the conventional metal-flow air secondary battery cannot flow, during the charging process, the metal plated to the negative electrode side forms a dendrite, which causes the metal to fail to form a uniform coating on the surface of the negative electrode, and is produced. Oxygen (O ₂ ) may cause disintegration damage of the ORR catalyst at the double effect electrode; the metal oxide generated during the discharge process will not only cover the surface of the negative electrode, causing anode passivation, but also contaminate the electrolyte. Increasing the ion conduction impedance may gradually evaporate and deplete under long-term operation, which affects the performance and life of the battery.

Therefore, it is necessary to provide a metal liquid flow air secondary battery to solve the problem of waste heat accumulation and the inability of the electrolyte to flow.

The invention provides a metal air liquid secondary battery, which can improve the performance and life of a metal air liquid secondary battery.

The invention provides another metal air flow secondary battery, which can greatly reduce the generation of bubbles to improve the performance and life of the metal air flow secondary battery.

The metal air flow secondary battery of the invention comprises a front casing, a discharge positive plate module, an air electrode module, a rear casing, a negative plate, a charging positive plate module and a middle casing. The front housing is formed by combining a first electrolyte channel module and a second electrolyte channel module, and has a first accommodating space for accommodating the electrolyte. The discharge positive plate module is located on the first side of the front casing, and includes a discharge positive plate having a plurality of first through openings, wherein the first electrolyte channel module is interposed between the discharge positive plate module and the second electrolyte channel module between. The air electrode module is located between the discharge positive plate module and the front casing, and includes an oxygen reduction reaction catalyst, which is in contact with the electrolyte. The rear housing is located on a second side of the front housing. The negative plate is located between the rear case and the front case and is in contact with the electrolyte. The charging positive plate module is located between the front casing and the negative plate, and includes a charging positive plate having a second through opening and an oxygen precipitation reaction catalyst. The middle casing is located between the charging positive plate module and the negative plate, and has a second accommodating space for accommodating the electrolyte.

Another metal air flow secondary battery of the present invention comprises a front casing, a discharge positive plate module, an air electrode module, a middle casing, a negative plate module, a charging positive plate module and a charging electrode module. The front housing is composed of a first electrolyte channel module and a second electrolyte channel module, and has a first accommodating space for accommodating the electrolyte. The discharge positive plate module is located on the first side of the front casing, and includes a discharge positive plate having a plurality of first through openings, wherein the first electrolyte channel module is interposed between the discharge positive plate module and the second electrolyte channel module between. The air electrode module is located between the discharge positive plate module and the front casing, and includes an oxygen reduction reaction catalyst, which is in contact with the electrolyte. The middle casing is located on the second side of the front casing and has a second accommodating space to accommodate the electrolyte. The negative plate module is located between the first side of the middle casing and the front casing, and has a third accommodating space for accommodating the deposition of the electrolyte and the generated metal. The charging positive plate module is located on the second side of the middle casing and includes a charging positive plate having a second through opening. The charging electrode module is located between the charging positive plate module and the middle casing, and has an oxygen precipitation reaction catalyst in contact with the electrolyte.

The above described features and advantages of the invention will be apparent from the following description.

The invention is further described in the following examples and the accompanying drawings, but the invention may be practiced in many different forms and should not be construed as being limited to the embodiments described herein. In the drawings, for the sake of clarity, the components and their relative sizes may not be drawn to the actual scale. In addition, the terms "including", "including", "having", etc. used in the text are all open terms; that is, including but not limited to. Moreover, the directional terms mentioned in the text, such as "upper", "lower", "left", "right", etc., are only used to refer to the direction of the schema. Therefore, the directional terminology used is for the purpose of illustration and not limitation.

Reference will now be made in detail to the exemplary embodiments embodiments Whenever possible, the same or similar component symbols are used in the drawings and description to refer to the same or the like.

1A is a perspective view showing an assembled structure of a metal-liquid flow air secondary battery in accordance with an embodiment of the present invention. Figure 1B is a rear perspective view of the structure of Figure 1A.

Referring to FIG. 1A and FIG. 1B , the metal-liquid secondary battery 10 of the present embodiment basically includes a plurality of battery cells 100 , and the discharge positive electrode collector plate 102 and the rechargeable positive electrode collector plate 104 are extended in the battery unit 100 . The negative electrode current collector plate 106 and the negative electrode current collector plate 108 are discharged. Further, a positive electrode end plate 110a and a negative electrode end plate 110b are respectively provided at both ends of the battery unit 100. The battery unit 100 described above forms a metal-air flow secondary battery 10 having a charge and discharge function.

When the discharge positive electrode current collector plate 102 and the discharge negative electrode current collector plate 106 are respectively connected to an external load (not shown), the metal air flow secondary battery 10 can perform a discharge operation. When the charging positive electrode current collecting plate 104 and the charging negative electrode current collecting plate 108 are respectively connected to an external load, the metal air flow secondary battery 10 can perform a charging operation.

In FIG. 1A, the positive electrode end plate 110a has, for example, an electrolyte outlet 112 penetrating the body thereof to discharge the electrolyte from the plurality of battery cells 100. In FIG. 1B, the negative electrode end plate 110b is disposed with an electrolyte inlet 116 passing through its body to supply electrolyte to a plurality of battery cells 100.

In addition, the positive electrode end plate 110a and the negative electrode end plate 110b can also be respectively disposed with a plurality of positioning holes 114a penetrating through the body thereof for assembly and positioning of the metal air flow secondary battery 10, and four positionings are used in this embodiment. Hole 114a. A plurality of screw holes 114b penetrating the main body of the positive electrode plate 110a and the negative electrode end plate 110b are respectively disposed. In the embodiment, 12 screw holes 114b are used to lock and fix the metal air flow secondary battery 10. Use.

2A is a schematic perspective view of a metal air flow secondary battery in accordance with another embodiment of the present invention. 2B is an exploded view of the assembled structure of the front side of the metal air flow secondary battery according to FIG. 2A. 2C is an exploded view of the assembled structure of the back surface of the metal-air flow secondary battery of FIG. 2B.

Referring to FIG. 2A and FIG. 2B , the metal air flow secondary battery of the embodiment may be the single battery unit 100 in the previous embodiment, which includes a discharge positive plate module 200 , an air electrode module 300 , and a front housing. 400. The charging positive plate module 500, the middle casing 600, the negative plate 700 and the rear casing 800.

In this embodiment, the front housing 400 can be a combination of the first electrolyte channel module 402 and the second electrolyte channel module 404, and has a first accommodating space for accommodating the electrolyte. In other words, the first side 400a of the front case 400 is the front side of the first electrolyte channel module 402, and the second side 400b of the front case 400 is the back side of the second electrolyte channel module 404. The discharge positive plate module 200 is located on the first side 400a of the front case 400; the air electrode module 300 is located between the discharge positive plate module 200 and the front case 400; and the rear case 800 is located at the second side of the front case 400. The side plate 400b is disposed between the rear case 800 and the front case 400, and the charging positive plate module 500 is located between the front case 400 and the negative plate 700; the middle case 600 is located at the charging positive plate module 500 and the negative electrode Between the boards 700.

In this embodiment, the discharge positive plate module 200 includes at least one discharge positive plate 202, wherein the discharge positive plate 202 may be a plate made of a highly conductive material having good electrical conductivity and corrosion resistance, such as stainless steel or nickel. (Ni).

The discharge positive electrode plate 202 has a front surface 202a facing the air side and a back surface 202b opposite to the front surface 202a, and the discharge positive electrode plate 202 includes a plurality of first through openings 204, and each of the first through openings 204 penetrates the front surface 202a of the discharge positive electrode plate 202. With the back surface 202b, the ambient air G can be allowed to pass through and reach the air electrode module 300.

Referring to FIG. 2B, the front surface 202a of the discharge positive electrode plate 202 (the surface away from the air electrode module 300) has protrusions 206a and 206b respectively disposed on the left and right sides of the first through opening 204 to respectively respectively The first through opening 204 is in communication. The projections 206a and 206b can form a plurality of air guiding channels for the reaction and cooling air required by the battery unit 100. In this way, the ambient air G can enter the first through opening 204 of the discharge positive electrode plate 202 from the protruding portion 206a (or the protruding portion 206b) by forced convection to supply oxygen required for the discharge reaction and take away the reaction. The waste heat generated by the process is then discharged from the discharge positive electrode plate 202 to the environment by the projection 206b (or the projection 206a).

Referring to FIG. 2C , in the back surface 202 b of the discharge positive plate 202 , the first groove 208 and the second groove 210 may be designed according to requirements, wherein the first groove 208 is disposed around the first through opening 204 . The second groove 210 is disposed around the first groove 208 to form a space with the air electrode module 300. Since the discharge positive plate module 200 can further include a sealing member 212, the first recess 208 can be formed with a space for accommodating the sealing member 212, but the structure of the discharge positive electrode plate of the present invention is not limited thereto. In addition, the discharge positive electrode plate module 200 may further include a discharge positive electrode collector plate 214 disposed on one side of the discharge positive electrode plate 202, wherein the discharge positive electrode collector plate 214 may be connected to the negative electrode plate 700 of the adjacent battery unit 100 to form a series connection. Discharge circuit.

Referring to FIG. 2B , the air electrode module 300 includes at least one air electrode 302 and a first isolation film 304 . The material of the first separator 304 may be a porous non-metal material such as polypropylene (PP), nylon (Nylon), Teflon (PTFE) or the like. The air electrode module 300 has a front surface 300a facing the discharge positive electrode plate module 200 and a rear surface 300b remote from the discharge positive electrode plate module 200. The air electrode 302 is located on the front surface 300a of the air electrode module 300.

The air electrode 302 is, for example, a porous conductive substrate (not shown), a waterproof gas permeable membrane (not shown) bonded to one side of the porous conductive substrate, and an oxygen reduction reaction contact bonded to the other side of the porous conductive substrate. The medium (discharge reaction catalyst) (not shown) is composed. The waterproof gas permeable membrane of the air electrode 302 faces the discharge positive electrode plate module 200. The first isolation film 304 is located on the back surface 300b of the air electrode module 300, wherein the oxygen reduction reaction catalyst faces the first isolation film 304 to be in contact with the electrolyte. In addition, the first isolation film 304 can isolate the metal generated during the charging reaction, directly contacts the oxygen reduction reaction catalyst of the air electrode 302, avoids causing the positive and negative electrodes to be short-circuited, and can also isolate the oxide-contaminated air electrode 302 generated by the discharge reaction. The oxygen reduction reaction catalyst can prolong the service life of the air electrode 302.

In this embodiment, when the battery unit 100 is assembled, the porous conductive substrate of the air electrode 302 can be in close contact with the first isolation film 304 and contact with the discharge positive electrode plate 202 of the discharge positive plate module 200 to form An electronic conduction path. When the ambient air G diffuses into the oxygen reduction reaction catalyst via the waterproof gas permeable membrane of the air electrode 302, a positive discharge reaction occurs. The waterproof gas permeable membrane of the air electrode 302 prevents the electrolyte from leaking into the environment.

Referring to FIG. 2B , the front case 400 of the present embodiment is a combination of the first electrolyte channel module 402 and the second electrolyte channel module 404 , but the invention is not limited thereto. The front housing 400 can also include other components. The first electrolyte channel module 402 and the second electrolyte channel module 404 may be an insulating frame structure, such as a square, but are not limited thereto. In this embodiment, the first electrolyte channel module 402 is interposed between the discharge positive plate module 200 and the second electrolyte channel module 404, wherein the second electrolyte channel module 404 has the first electrolyte The channel module 402 has a corresponding shape, and both the first electrolyte channel module 402 and the second electrolyte channel module 404 have substantially overlapping transverse sections.

In the present embodiment, the first electrolyte channel module 402 has a first opening 406 extending through the front surface 402a and the back surface 402b. The front surface 402a of the first electrolyte channel module 402 may further have a groove 408 disposed around the first opening 406. The size of the groove 408 is approximately equal to the peripheral boundary of the discharge positive plate 202, and the depth is approximately equal to the discharge positive plate. The thickness of 202. Therefore, the groove 408 can accommodate the combination of the discharge positive plate module 200 and the air electrode module 300 and can be sealed by a sealing member 410, and the electrolyte accommodated in the first opening 406 can contact the air electrode module 300. An ion conduction path is formed during the discharge reaction.

Referring to FIG. 2B and FIG. 2C , a second opening 412 and a third opening 414 are respectively disposed above and below the first opening 406 , wherein the second opening 412 and the third opening 414 respectively penetrate the first electrolyte channel module 402 . Front side 402a and back side 402b. In FIG. 2B, two sealing members 416 can be respectively disposed around the second opening 412 and the third opening 414 for sealing and sealing the electrolyte. The back surface 402b of the first electrolyte channel module 402 may have a distribution flow channel 418 that communicates between the first opening 406 and the second opening 412 and the first opening 406 and the third opening 414.

Referring to FIG. 2B , the second electrolyte channel module 404 has a fourth opening 420 , a fifth opening 422 and a sixth opening 424 corresponding to the respective openings of the first electrolyte channel module 402 , wherein the first opening 406 is defined by the first opening 406 . Forming a first intermediate rectangular opening 426 of the front case 400 with the fourth opening 420; forming a first electrolyte discharge channel 428 of the front case 400 by the second opening 412 and the fifth opening 422; by the third opening 414 and the The six openings 424 constitute a first electrolyte supply manifold 430 of the front housing 400. The first electrolyte supply manifold 430 and the first electrolyte discharge manifold 428 are respectively adjacent to the first intermediate rectangular opening 426, and may supply or discharge the electrolyte to deliver the electrolyte in each of the battery cells 100.

In addition, a groove 432 may be disposed on the surface of the second electrolyte channel module 404 facing the first electrolyte channel module 402, and is disposed on the outer periphery of the fourth opening 420, the fifth opening 422, and the sixth opening 424. The recess 432 can accommodate a seal 434 for sealing the electrolyte after assembly.

When the first electrolyte channel module 402 and the second electrolyte channel module 404 are combined into the front case 400, the first isolation film 304, the first electrolyte channel module 402, and the second electrolyte channel mode can be used. The group 404 is in close contact with the charging positive plate module 500, and defines a first accommodating space (not shown) for accommodating the electrolyte in the first intermediate rectangular opening 426. Moreover, the distribution flow channel 418 can communicate the first intermediate rectangular opening 426 with the first electrolyte discharge manifold 428 and the first intermediate rectangular opening 426 with the first electrolyte supply manifold 430 to supply the first electrolyte supply manifold The electrolyte in the 430 is delivered to the first accommodating space, and the electrolyte in the first accommodating space is output from the first electrolyte discharge manifold 428. Further, the electrolyte located in the first accommodating space can contact the first isolation film 304 of the air electrode module 300 and the charging positive electrode plate module 500 through the first intermediate rectangular opening 426, thereby providing ions in the battery unit 100. Conducting a path to perform a charge and discharge reaction.

In addition, referring to FIG. 2C, a groove 436 corresponding to the middle case 600 may be selectively disposed on the back surface (the second side 400b) of the second electrolyte channel module 404.

Then, in FIG. 2B, the charging positive plate module 500 includes at least a charging positive electrode plate 504 having a second through opening 502 and an oxygen evolution reaction catalyst (not shown). In the present embodiment, the charging positive electrode plate 504 may be a plate material made of a highly conductive material having good electrical conductivity and corrosion resistance, such as stainless steel or nickel (Ni). The charging positive plate module 500 may further include a second isolation film 506 disposed on a side of the charging positive plate 504 away from the front case 400 and facing the front case 400 for insulating metal generated during the charging reaction. The material of the second separator 506 is, for example, a porous non-metal material such as polypropylene (PP), nylon (Nylon), Teflon (PTFE) or the like.

Referring to FIG. 2C, the oxygen deposition reaction catalyst 508 of the rechargeable positive electrode plate module 500 faces the negative electrode plate 700, and the oxygen evolution reaction catalyst 508 is, for example, a stainless steel mesh. In addition, the charging positive plate module 500 may further include a charging positive electrode collector plate 510 disposed on one side of the charging positive electrode plate 504, and a negative electrode plate 700 connected to the adjacent battery cells to form a series charging circuit.

Referring to FIG. 2B , the middle casing 600 has an outer shape corresponding to the second electrolyte passage module 404 of the front casing 400 . In the present embodiment, the middle casing 600 is, for example, a square insulating frame, and the second electrolyte channel module 404 and the middle casing 600 both have substantially overlapping transverse sections. A second intermediate rectangular opening 602, a second electrolyte discharge manifold 604 and a second electrolyte supply manifold 606 for forming a second accommodating space are included in the middle casing 600, wherein the second electrolyte discharge manifold 604 A second intermediate rectangular opening 602 is adjacent to the second electrolyte supply manifold 606, respectively. The middle casing 600 is sealed with the charging positive plate module 500 and the negative plate 700 to define a second accommodating space for accommodating the electrolyte in the second intermediate rectangular opening 602 of the middle casing 600. The middle casing 600 may further include a groove 608 surrounding the outer edge of the second intermediate rectangular opening 602 and communicating with the second accommodating space for accommodating the charging positive plate module 500, and at the second intermediate rectangular opening 602. The electrolyte can contact the rechargeable positive plate module 500 to form an ion conduction path during the charging reaction. The size of the recess 608 is approximately equal to the peripheral boundary of the charging positive plate module 500, and the depth is approximately equal to the thickness of the charging positive plate module 500. Moreover, there is another recess 612 at the periphery of the recess 608 that can accommodate a seal 610, which can correspond to a recess 436 provided in the back of the second electrolyte channel module 404 (please refer to FIG. 2C).

Referring to FIG. 2B, two seals 614 can be respectively disposed around the second electrolyte discharge manifold 604 and the second electrolyte supply manifold 606 for post-assembly sealing of the electrolyte.

In the present embodiment, the negative electrode plate 700 is, for example, a plate material made of a highly conductive material having good electrical conductivity and corrosion resistance, such as stainless steel, nickel (Ni), tin (Sn), or any combination thereof. The negative electrode plate 700 may contact the electrolyte contained in the second intermediate rectangular opening 602 of the middle case 600 to perform a negative charge and discharge reaction.

Further, a discharge negative electrode current collecting plate 704 and a charging negative electrode current collecting plate 702 are provided on the lower side and the upper side of the negative electrode plate 700, respectively. When the charging negative current collector plate 702 is connected to the charging positive electrode plate 504 of the adjacent battery unit, a series charging circuit can be formed; when the discharging negative electrode current collecting plate 704 is connected to the discharging positive electrode plate 202 of the adjacent battery unit, a series discharge can be formed. Circuit.

With continued reference to FIG. 2B, the rear housing 800 has an outer shape corresponding to the middle housing 600. In the present embodiment, the rear case 800 is, for example, a square insulating frame, and both the middle case 600 and the rear case 800 have substantially overlapping transverse sections. The rear housing 800 can include a third electrolyte discharge manifold 802 and a third electrolyte supply manifold 804. In addition, the surface of the rear case 800 facing the negative plate 700 may be provided with a recess 806 for accommodating the negative plate 700. The peripheral boundary of the groove 806 is similar and slightly larger than the negative plate 700, and the depth thereof is approximately equal to the negative plate 700. The thickness. As such, when the negative electrode plate 700 is combined with the rear case 800, it can be brought into close contact with the negative electrode plate 700 by the recess 806.

In this embodiment, two seals 808 can be respectively disposed around the third electrolyte discharge manifold 802 and the third electrolyte supply manifold 804 for the purpose of sealing the electrolyte after assembly.

That is, in the assembled battery unit 100, the positions of the first electrolyte supply manifold 430, the second electrolyte supply manifold 606, and the third electrolyte supply manifold 804 are corresponding and in communication for the electrolyte The first and second accommodating spaces can flow into the charging and discharging reaction, and the positions of the first electrolyte discharging lane 428, the second electrolyte discharging lane 604, and the third electrolyte discharging lane 802 are also corresponding and connected. Therefore, the electrolyte can be discharged through the above-mentioned manifold.

If a plurality of battery cells 100 of FIG. 2A are combined, the rear case 800 of one of the adjacent two battery cells will be in contact with the discharge positive plate module 200 of the other battery cell.

3A is a schematic view showing a charging reaction working mechanism of the metal air flow secondary battery of FIG. 2B. In the case of a zinc-air secondary battery, in the charging process, an electrolyte composed of zinc oxide (ZnO), potassium hydroxide (KOH) and water (H ₂ O) is delivered to the battery via an external pump. Unit 100.

In FIG. 3A, the electrolyte first enters the third electrolyte supply manifold 804 of the rear housing 800, and then the electrolyte is introduced into the second intermediate rectangular opening 602 of the middle housing 600 via the second electrolyte supply manifold 606, and Further flowing into the second through opening 506 of the charging positive plate module 500 and the first intermediate rectangular opening 426.

When the electrolyte fills the first intermediate rectangular opening 426, the second through opening 506 and the second intermediate rectangular opening 602, the electrolyte can contact the air electrode of the air electrode module 300 and the second isolation film of the charging positive plate module 500. 506 and the negative electrode plate 700, and a conductive ion medium formed in the battery unit 100. In addition, the electrolyte also enters the second electrolyte supply manifold 606 of the middle casing 600 via the third electrolyte supply manifold 804, and then enters the first electrolyte supply manifold 430 of the front casing 400 to supply to the next. Battery unit.

In detail, each battery unit 100 can be charged by externally passing an appropriate current to the metal liquid flow air battery via the charging positive electrode current collecting plate 510 and the charging negative electrode current collecting plate 702. On the negative electrode side, zinc oxide (ZnO) and water (H ₂ O) in the electrolytic solution are co-reacted with e ^- introduced from the negative electrode current collector plate 702 of the negative electrode plate 700, and zinc oxide (ZnO) is further decomposed into Zinc ions (Zn ²⁺ ) migrate toward the negative electrode plate 700. After the zinc ions (Zn ²⁺ ) are contacted with the negative electrode plate 700, zinc ions (Zn ²⁺ ) can react with e ⁻ to form metallic zinc (Zn) and are plated onto the surface of the negative electrode plate 700. At the same time, hydroxide ions (OH ^- ) are also generated and migrate toward the second isolation film 506 of the charging positive plate module 500.

On the charged positive electrode side, when the hydroxide ion (OH ^- ) from the negative electrode contacts the second separator 506, the hydroxide ion (OH ^- ) can generate oxygen by the OER catalyst reaction on the stainless steel mesh (O ₂ ), water (H ₂ O) and e ^- . The negative electrode current collector plate 702 will be transmitted via a stainless steel net charge to the charge of the positive electrode plate 502 of the positive electrode current collector plate 510 and then into the adjacent cell 700 of the negative electrode plate 100 ^- e.

During the charging reaction, the electrolyte can be continuously circulated to allow oxygen (O ₂ ) to enter the first electrolyte discharge manifold 428 via the distribution flow path 418 with the electrolyte. Then, the electrolyte and O ₂ are sequentially flowed to the third electrolyte discharge lane 802 and the second electrolyte discharge manifold 604 of the next battery unit.

1A and 1B, the electrolyte and oxygen (O ₂ ) of each of the battery cells 100 can be discharged to the environment via the electrolyte outlet 112 of the metal flow air battery 10, or can be forced to convection by a fan. In an external environment. The electrolyte discharged from the electrolyte outlet 112 is again sent to the electrolyte inlet 116 via the external pump, thus completing the circulating flow of the electrolyte.

In addition, since the flowing electrolyte can prevent the metal zinc (Zn) from forming a dendritic structure on the surface of the negative electrode plate 700, the flowing electrolyte will also contribute to the formation of a uniform metal zinc (Zn) plating layer.

3B is a schematic view showing the discharge reaction working mechanism of the metal air flow secondary battery of FIG. 2B.

Referring to FIG. 3B, the working mechanism of the discharge reaction of the battery unit 100 is also exemplified by a zinc-air flow secondary battery. When the charging reaction is completed and the discharge reaction begins, the electrolyte is continuously circulated in a manner as described in the charging process to fill the respective intermediate rectangular openings, through the openings to form a conductive ion medium.

On the negative electrode side, metallic zinc (Zn) electroplated to the surface of the negative electrode plate 700 is co-reacted with hydroxide ions (OH ^- ) from the positive electrode. The generated zinc ions (Zn ²⁺ ) migrate from the negative electrode plate 700 toward the positive electrode, and e ^{− is} conducted from the negative electrode plate 700 to the discharge negative electrode collector plate 704, and then introduced into the discharge positive electrode plate 202 of the adjacent battery unit 100. The positive electrode collector plate 214 is discharged.

During the discharge reaction, the electrolyte can be continuously circulated to cause zinc oxide (ZnO) to flow out of the metal flow air battery with the electrolyte. That is, zinc oxide (ZnO) can be prevented from accumulating and covering the surface of the negative electrode plate 700. In addition, the zinc oxide (ZnO) present in the electrolyte can be removed by external filtration, so that the electrolyte can restore the original ion conductivity and then transport it to the metal flow air battery.

On the discharge positive electrode side, the ambient air G is, for example, a flow path formed by a fan forcedly convectively introduced into the projection 206a of the discharge positive electrode plate 202 and enters each of the first through openings 204, and then from the projections. The flow path formed by 206b is discharged to the environment. At the same time, oxygen (O ₂ ) can diffuse into the waterproof gas permeable membrane of the air electrode 302 and then enter the catalyst to react with water (H ₂ O) in the electrolyte and e ^- from the negative electrode to produce a negative electrode side. The migrated hydroxide ion (OH ^- ). Since the negative discharge reaction requires sufficient oxygen and generates a large amount of waste heat, air flow is required to supply the air to the negative side while meeting the reaction and heat dissipation requirements to ensure a stable performance output of the metal flow air battery.

The air flow rate required for the charge and discharge reaction of the above battery unit 100 can be estimated by the following formula: Where F _coolant is the air flow required for the reaction, I is the current (A), F is the Faraday constant (96485 C/mol), and N _cell is the number of cells.

In addition, a large amount of waste heat generated by the discharge reaction of the battery unit 100 can also be discharged by forced convection by a fan. The air flow required for heat dissipation can be estimated as follows: Among them, F _coolant is the air flow required for heat dissipation, I is current (A), V _o is open circuit voltage (V), V is operating voltage (V), ρ is air density (1.2kg/m ³ ), and C _P is The specific heat of the air (1000 J/kg/K), ΔT is the air inlet and outlet temperature difference (K), and N _cell is the number of batteries.

When the ambient air G is introduced into the first through opening 206 or the oxygen (O ₂ ) is discharged from the first through opening 206 by forced convection by a fan, an air flow field is generated on the surface of the discharge positive electrode plate to reduce air flow resistance and increase The effect of air and heat convection.

4A and 4B are simplified views of the working mechanism of the charge and discharge reaction, respectively, in accordance with FIGS. 3A and 3B.

Referring to FIG. 4A, the discharge positive electrode plate module 200, the charging positive electrode plate module 500, the negative electrode plate 700 and a space for accommodating the electrolyte are mainly shown. If a zinc-air battery is taken as an example, the reduction reaction of the negative electrode plate 700 and the positive electrode oxidation reaction during the charging process can be represented by the following chemical formulas respectively: Negative electrode reduction reaction: ZnO+H ₂ O+2e ^- → Zn+2OH ^- Positive electrode oxidation reaction: 2OH ^- → 1/2O ₂ +H ₂ O+2e ^-

It can be seen from the above chemical formula that zinc oxide (ZnO) water in the electrolyte of the negative electrode plate 700 is subjected to a reduction reaction together with electrons moving from the discharge positive electrode plate module 200 to the negative electrode plate 700 through an external circuit, and the generated zinc (Zn) is electroplated. To the surface of the metal of the negative electrode plate 700. The charging positive plate module 500 releases hydroxide ions (OH ^- ) into the electrolyte and migrates toward the discharge positive plate module 200. In addition, in the charging positive electrode plate module 500, when the hydroxide ions (OH ^- ) from the negative electrode plate 700 contact the charging positive electrode plate module 500, oxygen can be generated by the catalyst reaction on the charging positive electrode plate module 500 (O ₂ ), water and electronics. The electrons are conducted to the discharge positive plate module 200 and then moved to the negative plate 700 through the external circuit. Oxygen (O ₂ ) can be discharged via the charging positive plate module 500.

Referring to FIG. 4B, the negative electrode oxidation reaction and the positive electrode reduction reaction in the discharge process can be respectively represented by the following chemical formula: Negative electrode oxidation reaction: Zn + 2OH ^- → ZnO + H ₂ O + 2e ^- positive electrode reduction reaction: 1/2 O ₂ + H ₂ O + 2e ^- → 2OH ^-

It is known from the above chemical formula that zinc in the negative electrode plate 700 is oxidized together with hydroxide ions (OH ^- ) in the electrolytic solution, and zinc (Zn) in the negative electrode plate 700 is consumed, and zinc oxide is simultaneously produced ( ZnO), water and electrons. Among them, electrons move from the negative electrode plate 700 to the discharge positive electrode plate module 200 through the external circuit via the negative electrode plate 700. In addition, in the discharge positive electrode plate module 200, oxygen (O ₂ ) from the air is subjected to a reduction reaction together with water present in the electrolyte and electrons from the negative electrode plate 700 to generate hydroxide ions (OH ^- And moving toward the charging positive electrode plate module 500, and migrating from the discharge positive electrode plate module 200 to the negative electrode with the potassium hydroxide solution in the electrolytic solution as an ion conductive medium and participating in the above oxidation reaction.

In summary, the present invention has a discharge positive electrode, a charging positive electrode and a negative electrode configured three-pole metal air flow secondary battery, through the through opening in the discharge positive plate module and the charging positive plate module, The ambient air is introduced into the battery unit in a convective manner or the waste heat formed during the charging and discharging reaction is discharged, and the ambient air is not separately supplied for reaction and heat dissipation, which is advantageous for the weight reduction and cost reduction of the metal liquid flow air battery, system and operation Can be more simplified.

In detail, the present invention utilizes a three-pole metal air flow battery to help eliminate zinc oxide (ZnO) during discharge reaction to avoid negative passivation and electrolyte contamination, and to design air with a common air flow field design. Introducing the battery unit and taking away waste heat will help the battery to be compact, lightweight and reduce costs. In addition, in the charging reaction, it is advantageous to produce a uniform metal zinc (Zn) plating layer on the surface of the negative electrode, and to exclude oxygen (O ₂ ), and to avoid the negative effect of the generation of oxygen (O ₂ ) on the ORR catalyst. This provides good metal air flow battery performance and longevity.

In addition, the present invention provides an electrolyte supply manifold and an electrolyte discharge manifold in the front casing, the middle casing, and the rear casing, thereby providing a passage without excessively increasing the size of the battery unit, and connecting the interiors of the respective battery cells. To supply and discharge electrolyte. This provides good metal air flow battery performance and longevity.

Figure 5 is a perspective view showing an assembled structure of a metal-liquid flow air secondary battery in accordance with another embodiment of the present invention, wherein the same reference numerals as in Figures 1A and 1B are used to denote the same or similar members, and are omitted. For some technical descriptions, such as the size, material, function and the like of each module, reference may be made to the contents of FIG. 1A and FIG. 1B.

Referring to FIG. 5, the metal-liquid secondary battery 10A of the present embodiment basically includes a plurality of battery cells 100A, a charging positive electrode collector plate 104, a discharge positive electrode collector plate 102, a charging negative electrode collector plate 108, and a discharge negative electrode set. The electric board 106, the front end board 111a and the rear end board 111b. A plurality of battery cells 100A are arranged in a stacked manner in series. When the charging positive electrode current collecting plate 104 and the charging negative electrode current collecting plate 108 are respectively connected to an external load, the metal liquid flow air secondary battery 10A can perform a charging operation, at which time the charging positive electrode current collecting plate 510 in each of the battery cells 110A is The charged negative current collector plates 707 of the adjacent battery cells 110A are connected in series by an external connection (not shown in FIG. 5). When the discharge positive electrode collector plate 102 and the discharge negative electrode collector plate 106 are respectively connected to an external load, the metal liquid flow air secondary battery 10A can perform a discharge operation, at which time the discharge positive electrode collector plate 214 in each of the battery cells 110A is The discharge negative electrode collector plates 706 of the adjacent battery cells 110A are connected in series by external connection. The front end plate 111a is disposed through an electrolyte inlet (not shown) of its body to supply electrolyte to a plurality of battery cells 100A. The rear end plate 111b is disposed through the electrolyte outlet 112 of its body to discharge the electrolyte from the plurality of battery cells 100A. In addition, the front end plate 111a and the rear end plate 111b are respectively disposed with a plurality of positioning holes 114a penetrating through the main body thereof for assembly and positioning of the battery. In the embodiment, four positioning holes 114a are used. The front end plate 111a and the rear end plate 111b are also respectively disposed with a plurality of screw holes 114b penetrating the main body thereof. In the present embodiment, twelve screw holes 114b are used for locking and fixing the metal liquid air secondary battery 10A.

6A is a perspective view of a metal air flow secondary battery according to another embodiment of the present invention, and FIG. 6B is an exploded view of the assembled structure of the front surface of the metal air flow secondary battery according to FIG. 6A, FIG. 6C Is an exploded view of the assembled structure of the back side of the metal-air flow secondary battery of FIG. 6B, wherein the same reference numerals as those of FIGS. 2A, 2B, and 2C are used to denote the same or similar members, and a part of the technical description is omitted. For example, the dimensions, materials, functions, and the like of each module can be referred to the contents of FIGS. 2A, 2B, and 2C.

Referring to FIGS. 2A to 2C and FIGS. 6A to 6C, the battery unit 100A of the present example is similar to the battery unit 100 of the previous embodiment. It should be noted that the relative positions of the discharge positive plate module 200A, the negative plate module 700-1, and the charged positive plate module 500 of the battery unit 100A of the present embodiment are the same as those of the battery unit 100 of the previous embodiment. The relative positions of the plate module 200, the negative plate module 700, and the charging positive plate module 500 are different.

Referring to FIG. 6B and FIG. 6C, the battery unit 100A of the present embodiment includes a discharge positive plate module 200A. The discharge positive plate module 200A includes a discharge positive plate 202 and a seal 212. The discharge positive electrode plate 202 has a front surface 202a and a back surface 202b opposite to the front surface 202a, and the sealing member 212 is disposed on the back surface 202b of the discharge positive electrode plate 202. A plurality of first through openings 204 extend through the front surface 202a and the back surface 202b of the discharge positive electrode plate 202. The discharge positive electrode plate 202 has a projection 206a and a projection 206b which are disposed on the front surface 202a. The protruding portion 206a and the protruding portion 206b are respectively disposed on the left side and the right side of the adjacent plurality of first through openings 204 to communicate with the respective first through openings 204. The protruding portion 206a and the protruding portion 206b are disposed on a surface away from the air electrode module 300, and can form a plurality of air guiding channels for reacting and dissipating air required by the battery unit 100A. In this way, the ambient air G can enter the plurality of first through openings 204 of the discharge positive plate 202 from the protruding portion 206a (or the protruding portion 206b) by forced convection to supply oxygen required for the discharge reaction and take away The waste heat generated by the reaction process is then discharged to the discharge positive electrode plate 202 by the projections 206b (or the projections 206a) to the environment.

The discharge positive electrode plate 202 also has a first recess 208 disposed on the back surface 202b of the discharge positive electrode plate 202. The first groove 208 is disposed around the plurality of first through openings 204 to form a space in which the seal 212 can be received. The discharge positive electrode plate 202 further has a second recess 210 disposed on the back surface 202b of the discharge positive electrode plate 202. The second groove 210 is disposed around the first groove 208 to form a space that can accommodate the air electrode module 300. The discharge positive current collector plate 214 is selectively disposed on one side of the discharge positive electrode plate 202, wherein the discharge positive electrode current collector plate 214 can be connected to the negative electrode plate module 700-1 of the adjacent battery unit 100A to form a series discharge circuit. .

It is to be noted that the discharge positive electrode plate module 200A of the present embodiment further includes a separator 216 disposed on a side of the discharge positive electrode plate 202 away from the front case 400-1. The separator 216 can isolate the discharge positive electrode plate 202 of the discharge positive electrode plate module 200A of the battery unit 100A and the charging positive electrode plate module 500 of the adjacent battery unit 100A, so that the discharge positive electrode plate module of the adjacent two battery cells 100A The group 200A and the charging positive plate module 500 are insulated.

The battery unit 100A includes an air electrode module 300 between the discharge positive plate module 200 and the front housing 400-1, and includes an air electrode 302 and a first isolation film 304. The air electrode module 300 has a front surface 300a facing the discharge positive electrode plate module 200 and a rear surface 300b facing the front surface 300a. The air electrode 302 is disposed on the front surface 300a of the air electrode module 300, and the first isolation film 304 is disposed on the back surface 300b of the air electrode module 300 to be positioned between the air electrode 302 and the front case 400-1 after assembly. The air electrode 302 is composed of a porous conductive substrate (not shown), a waterproof gas permeable membrane (not shown) bonded to one surface of the porous conductive substrate, and an oxygen reduction reaction bonded to the other side of the porous conductive substrate. Catalyst (discharge reaction catalyst) (not shown). The waterproof gas permeable membrane of the air electrode 302 faces the discharge positive electrode plate module 200A, and the oxygen reduction reaction catalyst faces the first isolation film 304 to be in contact with the electrolyte. The ambient air G entering the plurality of first through openings 204 of the discharge positive electrode plate 202 can diffuse into the oxygen reduction reaction catalyst through the waterproof gas permeable membrane of the air electrode 302 to perform a discharge reaction, and the waterproof gas permeable membrane can also avoid the electrolyte solution. Leak to the environment. In addition, the first isolation film 304 can isolate the metal generated by the charging reaction and directly contact the oxygen reduction reaction catalyst of the air electrode 302 to avoid the occurrence of a short circuit between the positive and negative electrodes, and it can also isolate the oxide generated by the discharge reaction from contaminating the air electrode 302. The oxygen reduction reaction catalyst extends the life of the air electrode 302.

The battery unit 100A includes a front housing 400-1 which is a combination of a first electrolyte channel module 402 and a second electrolyte channel module 404. In this embodiment, the first electrolyte channel module 402 is interposed between the discharge positive plate module 200A and the second electrolyte channel module 404, wherein the second electrolyte channel module 404 has the first electrolyte The channel module 402 has a corresponding shape, and both the first electrolyte channel module 402 and the second electrolyte channel module 404 have substantially overlapping transverse sections.

The first electrolyte channel module 402 in the front housing 400-1 has a first opening 406 extending through the front surface 402a and the back surface 402b. A recess 408 can be disposed in the front side 402a of the first electrolyte channel module 402. The groove 408 is disposed around the first opening 406. The size of the recess 408 is approximately equal to the peripheral boundary of the discharge positive plate 202, and the depth is approximately equal to the thickness of the discharge positive plate 202. Therefore, the groove 408 can accommodate the combination of the discharge positive plate module 200A and the air electrode module 300 and can be sealed by the sealing member 410, and the electrolyte accommodated in the first opening 406 can contact the air electrode module 300. An ion conduction path is formed during the discharge reaction. The first electrolyte channel module 402 has a second opening 412 and a third opening 414 respectively above and below the first opening 406 , wherein the second opening 412 and the third opening 414 respectively penetrate the first electrolyte channel module 402 . Front side 402a and back side 402b. In FIG. 6B, two sealing members 416 can be respectively disposed around the second opening 412 and the third opening 414 for sealing and sealing the electrolyte. The back surface 402b of the first electrolyte channel module 402 may have a first opening 406 and a second opening 412 (or the first intermediate rectangular opening 426 and the first electrolyte discharge channel 428) and the first opening 406 and the first opening A plurality of electrolyte distribution channels 418 of three openings 414 (or first intermediate rectangular opening 426 and first electrolyte supply manifold 430).

It should be noted that, in this embodiment, the first electrolyte channel module 402 further has a recess 413 disposed on the back surface 402b. The groove 413 is disposed around the first opening 406, the second opening 412, and the third opening 414 to form a space in which the sealing member 415 can be received.

The second electrolyte channel module 404 has a fourth opening 420, a fifth opening 422 and a sixth opening 424 corresponding to the first opening 406, the second opening 412 and the third opening 414 of the first electrolyte channel module 402, respectively. . The first opening 406 and the fourth opening 420 constitute a first intermediate rectangular opening 426 of the front case 400-1 to form a first accommodating space. The second opening 412 and the fifth opening 422 constitute a first electrolyte discharge manifold 428 of the front case 400-1. The third opening 414 and the sixth opening 424 constitute a first electrolyte supply manifold 430 of the front case 400-1. The first electrolyte supply manifold 430 and the first electrolyte discharge manifold 428 are adjacent to the first intermediate rectangular opening 426, respectively, and can transport the electrolyte in the first electrolyte supply manifold 430 to the first accommodation. The space and the electrolyte in the first accommodating space are output from the first electrolyte discharge manifold 428 to transport the electrolyte in each of the battery cells 100A.

It should be noted that, in this embodiment, the recess 432 and the sealing member 434 of FIG. 2B may not be disposed on the front surface 404a of the second electrolyte channel module 404 facing the first electrolyte channel module 402.

Additionally, a recess 436 can be selectively provided on the back side 404b (second side 400b) of the second electrolyte channel module 404. The groove 436 is disposed around the fourth opening 420. It is to be noted that the recess 436 can accommodate a seal 417 for use in sealing the electrolyte after assembly. The size of the recess 436 is approximately equal to the peripheral boundary of the negative plate module 700-1, and the depth thereof is approximately equal to half the thickness of the negative plate module 700-1. In this way, the recess 436 can accommodate the negative plate module 700-1, and the electrolyte in the recess 436 can contact the negative plate module 700-1 to form an ion conduction path during the charge and discharge reaction. In addition, in FIG. 6B, two grooves 439 are selectively disposed on the back surface 404b (second side 400b) of the second electrolyte channel module 404, respectively disposed around the fifth opening 422 and the sixth opening 424. around. Two seals 438 are respectively disposed on the two grooves 439 for the purpose of sealing the electrolyte after assembly.

When the first electrolyte channel module 402 and the second electrolyte channel module 404 are combined into the front case 400-1, the first electrolyte channel module 402, the second electrolyte channel module 404, and the negative electrode can be used. The plate module 700-1 is tightly closed, a gap is formed between the first isolation film 304 and the negative plate module 700-1 to allow the electrolyte to flow, and a first intermediate rectangular opening 426 defines one for accommodating the electrolysis. The first accommodation space of the liquid (not shown). And, the electrolyte distribution flow path 418 can communicate with the first intermediate rectangular opening 426 and the first electrolyte discharge manifold 428 and the first intermediate rectangular opening 426 and the first electrolyte supply manifold 430 to supply the first electrolyte The electrolyte in the manifold 430 is delivered to the first accommodating space, and the electrolyte in the first accommodating space is output from the first electrolyte discharge manifold 428. Further, the electrolyte located in the first accommodating space can be in contact with the first isolation film 304 and the negative plate module 700-1 of the air electrode module 300 through the first intermediate rectangular opening 426, and further in the battery unit 100A. An ion conduction path is provided to perform a charge and discharge reaction.

The battery unit 100A includes a negative plate module 700-1. The negative plate module 700-1 is located between the first side of the middle casing 600-1 and the front casing 400-1, and has a third accommodating space for accommodating the deposition of the electrolyte and the generated metal. In the present embodiment, the negative electrode plate module 700-1 includes a negative electrode plate 700A and a porous metal material 701. The negative electrode plate 700A has a front surface 700a facing the second electrolyte passage module 404 and a reverse surface 700b opposite to the front surface 700a. The intermediate rectangular opening 700c penetrates the front side 700a and the reverse side 700b of the negative electrode plate 700A, and the intermediate rectangular opening 700c can accommodate the porous metal material 701. The negative electrode plate 700A has a first flange 700d and a second flange 700e, and is disposed around the intermediate rectangular opening 700c, and is disposed on the front surface 700a and the reverse surface 700b of the negative electrode plate 700A, respectively. The peripheral boundaries of the first flange 700d and the second flange 700e are respectively equal to the fourth opening 420 of the second electrolyte channel module 404 and the opening 630c of the third electrolyte channel module 630. The height between the first flange 62 and the second flange 63 is approximately equal to the thickness of the porous metal material 701. The porous metal material 701 has a plurality of pores to serve as a third accommodating space of the negative electrode plate module 700-1. The negative plate module 700-1 further includes a clip 703 and a clip 705 which are respectively coupled to the first flange 700d and the second flange 700e of the negative plate 700A. The distance between the clip 703 and the clip 705 is smaller than the thickness of the porous metal material 701. As such, the porous metal material 701 can be fixed and clamped by the two clips 703, 705 to form a good electron conduction path between the negative electrode plate 700A and the porous metal material 700.

The negative electrode plate module 700-1 further includes a discharge negative electrode current collector plate 706 disposed on one side of the negative electrode plate 700A (for example, but not limited to, an upper right side). The discharge negative electrode collector plate 706 can be connected to the discharge positive electrode collector plate 214 of the adjacent battery unit 100A to form a series discharge circuit. The negative plate module 700-1 further includes a charging negative current collecting plate 707 disposed on one side of the negative electrode plate 700A (for example, but not limited to: the lower right side). The charging negative current collector plate 707 can be connected to the charging positive current collector plate 510 of the adjacent battery unit 100A to form a series charging circuit.

In addition, the first flange 700d and the second flange 200e of the negative electrode plate 700A are respectively disposed on a first pseudo plane (not shown) and a second pseudo plane (not shown). The front case 400-1, the negative plate 700A and the middle case 600-1 are stacked in a stacking direction, and the first pseudo plane (not shown) and the second pseudo plane (not shown) are in the stacking direction. The distance is approximately equal to the sum of the depth of the recess 436 of the second electrolyte channel module 404 and the depth of the recess 634 of the third electrolyte channel module 630. When the electrolyte enters the porous metal material 701 from the first intermediate rectangular opening 426 of the front case 400, respectively, a metal (for example, but not limited to: zinc) generated during the charging process may be deposited on the pores of the porous metal material 701 (ie, the negative electrode). The third housing space of the panel module 700-1 is used as a metal for later discharge.

The battery unit 100A includes a middle case 600-1 located at the second side 400b of the front case 400-1 and having a second accommodating space to accommodate the electrolyte. Specifically, the middle casing 600-1 of the present embodiment includes a third electrolyte channel module 630 and a fourth electrolyte channel module 640.

The third electrolyte channel module 630 has a front surface 630a facing the negative electrode plate module 700-1 and a back surface 630b opposite to the front surface 630a. The third electrolyte channel module 630 has a seventh opening 630c, an eighth opening 630d and a ninth opening 630e, both of which extend through the front surface 630a and the reverse surface 630b of the third electrolyte channel module 630. The seventh opening 630c can accommodate the electrolyte. The eighth opening 630d and the ninth opening 630e are located above the seventh opening 630c and below the seventh opening 630c, respectively. In the front surface 630a of the third electrolyte channel module 630, the groove 634 is disposed around the seventh opening 630c (or the second intermediate rectangular opening 602) and is approximately equal to the peripheral boundary of the negative plate module 700-1, and the groove The depth of 634 is approximately equal to half the thickness of the negative plate 700A. In this way, the recess 634 can accommodate the negative plate module 700-1 and communicate with the second receiving space, and the electrolyte in the seventh opening 630c can contact the negative plate module 700-1 to form the charging. The ion conduction path during the discharge reaction.

The third electrolyte channel module 630 further includes a seal 631, a seal 632 and a seal 633. At the front side 630a of the third electrolyte passage module 630, a groove 635 is disposed at a peripheral boundary of the groove 634 to form a space in which the seal 631 can be accommodated. In the front surface 630a of the third electrolyte channel module 630, the groove 636 and the groove 637 are respectively disposed around the eighth opening 630d and around the ninth opening 630e to form a seal 632 and a seal 633 respectively. Space.

The fourth electrolyte channel module 640 has a front surface 640a facing the negative electrode plate module 700-1 and a reverse surface 640b opposite to the front surface 640a. The fourth electrolyte channel module 640 has a tenth opening 640c, an eleventh opening 640d and a twelfth opening 640e, all of which penetrate the front surface 640a and the reverse surface 640b of the fourth electrolyte channel module 640, and respectively correspond to and communicate with the first The seventh opening 630c, the eighth opening 630d and the ninth opening 630e of the three electrolyte channel module 630. The tenth opening 640c can accommodate the electrolyte. The eleventh opening 640d and the twelfth opening 640e are located above the tenth opening 640c and below the tenth opening 640c, respectively. The seventh opening 630c of the third electrolyte channel module 630 and the tenth opening 640c of the fourth electrolyte channel module 640 constitute a second intermediate rectangular opening 602 of the middle casing 600-1 to define one for accommodating the electrolysis The second accommodating space of the liquid (not shown). The eighth opening 630d of the third electrolyte channel module 630 and the eleventh opening 640d of the fourth electrolyte channel module 640 constitute a second electrolyte discharge manifold 604 located above the second intermediate rectangular opening 602. The ninth opening 630e of the third electrolyte channel module 630 and the twelfth opening 640e of the fourth electrolyte channel module 640 constitute a second electrolyte supply manifold 606 located below the second intermediate rectangular opening 602. The second electrolyte supply manifold 606 and the second electrolyte outlet manifold 604 may be adjacent to the second intermediate rectangular opening 602, respectively, and form a supply and discharge channel for the electrolyte to deliver the electrolyte. Wherein, the positions of the first electrolyte supply manifold 430 and the second electrolyte supply manifold 606 are corresponding and in communication, and the positions of the first electrolyte discharge manifold 428 and the second electrolyte discharge manifold 604 are corresponding and connected. of.

At the front side 640a of the fourth electrolyte channel module 640, a distribution flow path 648 is disposed between the opening 640c and the opening 640d and between the opening 640c and the opening 640e. As such, the electrolyte can enter the second intermediate rectangular opening 602 from the electrolyte supply manifold 606 via the distribution flow passage 648 and to the electrolyte discharge manifold 604 via the distribution flow passage 648.

At the front surface 640a of the fourth electrolyte passage module 640, a groove 644 is disposed around the tenth opening 640c, the eleventh opening 640d, and the twelfth opening 640e to form a space in which the seal 646 can be received. On the reverse side 640b of the fourth electrolyte channel module 640, the groove 645 is disposed around the tenth opening 640c and is approximately equal to the peripheral boundary of the charging electrode 910 of the charging electrode module 900, and the depth of the groove 645 is approximately equal to The thickness of the charging electrode 910. In this way, the groove 645 can accommodate the combination of the charging electrode 910 and the isolation film 920, and the electrolyte in the tenth opening 640c can contact the charging electrode module 900 to form an ion conduction path during the charging reaction. In addition, in the reverse surface 640b of the fourth electrolyte channel module 640, the groove 647, the groove 649a and the groove 649b are respectively disposed around the tenth opening 640c, the eleventh opening 640d and the twelfth opening 640e to form The space of the seal 641, the seal 642 and the seal 643 can be accommodated separately.

The charging positive plate module 500-1 of the present embodiment is located on the second side of the middle casing 600-1, and includes a charging positive plate 504 and a sealing member 508a having a second through opening 501. The charging positive plate 504 has a reverse side 500b facing the air side and a front side 500a opposite to the reverse side 500b, and the sealing member 508a is disposed on the front side 500a of the charging positive plate 504. A plurality of second through openings 501 extend through the front surface 500a and the back surface 500b of the charging positive electrode plate 504. The reverse surface 500b of the charging positive electrode plate 504 has a protruding portion 503a and a protruding portion 503b, which are respectively disposed on the left and right sides of the second through opening 501 to communicate with the respective second through openings 501. The protruding portion 503a and the protruding portion 503b are disposed on a surface away from the charging electrode module 900 to form a guiding flow path for generating oxygen generated by the battery unit 100A. The oxygen leaving from the plurality of second through openings 501 of the charging positive electrode plate 504 can be discharged to the environment from the protruding portion 503a (or the protruding portion 503b) by forced convection. That is, the oxygen generated by the charging reaction can be smoothly discharged outside the battery unit 100A, and the inside of the battery unit 100A is less likely to accumulate air bubbles, and the reaction area is reduced. Thereby, the performance of the battery unit 100A can be improved.

On the surface of the charging positive electrode plate 504 facing the middle casing 600-1 (i.e., the front surface 500a of the charging positive electrode plate 504), a recess 505 of a charging positive electrode plate 504 is disposed around the plurality of second through openings 501 to form The space for the seal 508a can be accommodated. At the front side 500a of the charging positive electrode plate 504, a recess 507 of the charging positive electrode plate 504 is disposed around the recess 505 to form a space in which the charging electrode module 900 can be accommodated. The charging positive current collector plate 510 is disposed on one side of the charging positive electrode plate 504 (for example, but not limited to: the lower right side), and the charging positive electrode current collecting plate 510 of one battery unit 100A is connectable to the adjacent another battery unit 100A. The negative current collector plate 707 is charged and connected to the negative electrode plate module 700-1 to form a series charging circuit.

The charging electrode module 900 is located between the charging positive plate module 500-1 and the middle casing 600-1. The charging electrode module 900 includes a charging electrode 910, a third isolation film 920, and an oxygen evolution reaction catalyst (not shown). The charging electrode module 900 has a reverse surface 900b facing the charging positive plate module 500-1 and a front surface 900a opposite to the reverse surface 900b. The charging electrode 910 is disposed on the reverse surface 900b of the charging electrode module 900, and the third isolation film 920 is disposed on the front surface 900a of the charging electrode module 900. The charging electrode 910 is composed of a porous conductive material for charging reaction and a waterproof gas permeable membrane bonded to one surface of the porous conductive material, wherein the waterproof gas permeable membrane of the charging electrode 910 is facing the charging positive electrode plate module 500- 1. The oxygen generated by the charging electrode 910 can diffuse into the plurality of second through openings 501 of the charging positive electrode plate 504 through the waterproof gas permeable membrane to be discharged to the environment, and the waterproof gas permeable membrane of the charging electrode 910 can also prevent the electrolyte from leaking to the environment. In addition, the third isolation film 920 can isolate the metal generated by the charging reaction (such as, but not limited to, zinc) from directly contacting the porous conductive material of the charging electrode 910 to avoid the occurrence of a short circuit between the positive and negative electrodes. In addition, the third isolation film 920 can also isolate the oxide generated by the discharge reaction from contaminating the porous conductive material of the charging electrode 910 to extend the service life of the charging electrode 910. The oxygen evolution reaction catalyst is disposed between the charging electrode 910 and the fourth electrolyte channel module 640 to contact the electrolyte to catalyze the charging reaction.

Fig. 7A is a schematic view showing the charging reaction working mechanism of the metal-air flow secondary battery of Fig. 6B. FIG. 8A is a simplified diagram of the working mechanism of the charging reaction illustrated in FIG. 7A. In the case of a zinc-air secondary battery, in the charging process, an electrolyte composed of zinc oxide (ZnO), potassium hydroxide (KOH) and water (H ₂ O) is transported to the molten metal via an external pump. The electrolyte inlet (not shown) of the air secondary battery 10A is then sequentially distributed to each of the battery cells 100A. In each of the battery cells 100A, the electrolyte first enters the second electrolyte supply manifold 606 of the middle casing 600-1, and the electrolyte also enters the first electrolyte supply manifold 430 of the front casing 400-1, respectively. The distribution flow channel 648 of the fourth electrolyte channel module 640 and the distribution flow channel 418 of the first electrolyte channel module 402 are introduced into the second intermediate rectangular opening 602 of the middle casing 600-1 and the front casing 400-1. The first intermediate rectangular opening 426; then, flows to the intermediate rectangular opening 700c of the negative plate 700A of the negative plate module 700-1, and then flows into the pores of the porous metal material 701. When the electrolyte fills the second intermediate rectangular opening 602 of the middle casing 600-1, the first intermediate rectangular opening 426 of the front casing 400-1, and the intermediate rectangular opening 700c of the negative plate 700A, the electrolyte can contact the air electrode module. The air electrode 302 of 300, the charging electrode 910 of the charging electrode module 900 and the porous metal material 701 of the negative electrode plate module 700-1, and the conductive ion medium formed in the battery unit 100A.

Each of the battery cells 100A can be charged by externally passing an appropriate current from the charged positive electrode current collector 104 of the metal liquid flow air secondary battery 10A and the charged negative electrode current collector 108. On the negative electrode side of the battery cell 100A, zinc oxide (ZnO) and water (H ₂ O) in the electrolytic solution are co-reacted with e ^- introduced from the negative electrode current collector plate 707 of the negative electrode plate 700A, and zinc oxide (ZnO) Further, it is decomposed into zinc ions (Zn ²⁺ ) and migrates toward the porous metal material 701. After the zinc ion (Zn ²⁺ ) contacts the porous metal material 701, the zinc ion (Zn ²⁺ ) can react with e ⁻ to form zinc (Zn) and deposit into the pores of the porous metal material 701 . At the same time, hydroxide ions (OH ^- ) are also generated and migrate toward the charging electrode 910 of the charging electrode module 900. On the charged positive electrode side, when the hydroxide ion (OH ^- ) from the negative electrode side contacts the charging electrode 910, the hydroxide ion (OH ^- ) will react to generate oxygen (O ₂ ), water (H ₂ O) and e. ^- . e ^- is conducted to the charging positive electrode collector plate 510 of the charging positive electrode plate 504 via the charging electrode 910, and then introduced to the charging negative electrode current collecting plate 707 of the negative electrode plate 700A of the adjacent battery cell 100A.

In particular, oxygen (O ₂ ) generated via the charging electrode 910 can be diffused into the plurality of second through openings 501 of the charging positive plate 504 via the waterproof gas permeable membrane of the charging electrode module 900, and then discharged by forced convection by a fan. To the environment. In this way, the problem that the generated oxygen (O ₂ ) may accumulate in the battery unit 100A so that the electrolyte cannot effectively contact the charging electrode 910 can be solved, thereby improving the performance of the metal air current battery 10A.

The electrolyte in the first intermediate rectangular opening 426 and the second intermediate rectangular opening 602 passes through the electrolyte distribution flow path 418 of the first electrolyte channel module 402 and the electrolyte distribution flow path 648 of the fourth electrolyte channel module 640. The first electrolyte discharge manifold 428 of the front housing 400-1 and the second electrolyte discharge manifold 604 of the middle housing 600-1 are entered. As a result, the electrolyte of each of the battery cells 100A can be discharged to the outside through the electrolyte outlet 112 of the metal-flow air secondary battery 10A. The electrolyte discharged from the electrolyte outlet 112 is again sent to the electrolyte inlet (not shown) via the external pump, thus completing the circulating flow of the electrolyte.

Fig. 7B is a schematic view showing the discharge reaction working mechanism of the metal-air flow secondary battery of Fig. 6B. FIG. 8B is a simplified diagram of the working mechanism of the discharge reaction illustrated in FIG. 7B. When the charging reaction is completed and the discharge reaction begins, the electrolyte is continuously circulated in a manner as described in the charging process to fill the intermediate rectangular openings 426, 602, 700c to form an ion-conducting medium. On the negative electrode side, zinc (Zn) deposited to the pores of the porous metal material 701 reacts with hydroxide ions (OH ^- ) from the positive electrode side. The generated zinc ions (Zn ²⁺ ) migrate from the porous metal material 701 toward the positive electrode side, and e ^{− is} conducted from the negative electrode plate 700A to the discharge negative electrode collector plate 706, and then introduced into the discharge positive electrode plate 202 of the adjacent battery unit 100A. The discharge positive electrode collector plate 214. Zinc ion (Zn ²⁺ ) will further react with hydroxide ion (OH ^- ) to produce zinc oxide (ZnO) and water (H ₂ O), while zinc oxide (ZnO) which is partially insoluble in the electrolyte will be solid. The form exists in the pores or electrolyte of the porous metal material 701. The production of zinc oxide (ZnO) of this solid not only covers the porous metal material 701 so as to cause passivation of the negative electrode, but also contaminates the electrolyte so as to increase the ion conduction resistance. These two phenomena respectively cause the negative discharge reaction and ion conduction to deteriorate, so the battery performance will be degraded or even stopped. To overcome this problem, during the discharge reaction, the electrolyte can be continuously circulated to cause the zinc oxide (ZnO) to be discharged from the molten metal secondary battery 10A with the electrolyte. In this way, zinc oxide (ZnO) accumulation and negative passivation can be avoided. Further, zinc oxide (ZnO) present in the electrolytic solution can be removed by an external filtration method, so that the electrolyte can restore the original ion conductivity and then transport it to the metal liquid flow air secondary battery 10A. On the positive side of the discharge, air can be forced into a plurality of first through openings 204 of the discharge positive plate 202 by a fan in a forced convection manner, and then discharged to the environment. At the same time, oxygen (O ₂ ) can diffuse into the waterproof gas permeable membrane of the air electrode 302 and then enter the catalyst to react with water (H ₂ O) in the electrolyte and e ⁻ from the negative electrode side to generate a negative electrode. Side-migrating hydroxide ion (OH ^- ). Since the negative discharge reaction requires sufficient oxygen and generates a large amount of waste heat, it is necessary to consider whether the air flow can simultaneously satisfy the reaction and heat dissipation requirements when supplying the air to the negative electrode side to ensure that the battery unit 100A can produce a stable output.

In summary, in the embodiment, the discharge positive plate module 200A is located on the first side of the front case 400-1, and the middle case 600-1 is located on the second side of the front case 400-1. The group 700-1 is located between the first side of the middle case 600-1 and the front case 400-1, and the charging positive plate module 500-1 is located at the second side of the middle case 600-1, and the charging electrode module 900 is located between the charging positive plate module 500-1 and the middle casing 600-1. Therefore, oxygen can be effectively discharged by the fan, and the liquid level of the electrolyte can be maintained stable, that is, the reaction area of the battery unit 100A is substantially maintained. constant. As a result, the charging voltage of the metal-air flow secondary battery 10A can be stabilized, and the discharge voltage and the coulombic efficiency can be improved, which will be described below with reference to FIG.

Figure 9 is a graph showing the voltage versus time of a metal-air flow secondary battery 10A according to another embodiment of the present invention, wherein a curve S15 shows the voltage of the metal-air flow secondary battery 10A in the case where the charging time is 15 minutes. The relationship of time, the curve S30 shows the relationship between the voltage of the metal-air flow secondary battery 10A and the time in the case where the charging time is 30 minutes, and the curve S60 shows the second time of the metal-air flow in the case where the charging time is 60 minutes. The relationship between the voltage of the battery 10A and time. Referring to FIG. 9, the charging voltage of the metal air flow secondary battery 10A can be maintained stable between 2.00 and 2.13 V for a long time; the discharge voltage of the metal air flow secondary battery 10A can be raised to 0.90 to 0.55 V; The coulombic efficiency of the liquid secondary battery 10A can be increased by 81% to 90%.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

10, 10A‧‧‧Metal air current battery

100, 100A‧‧‧ battery unit

102‧‧‧Discharge positive current collector board

104‧‧‧Charging positive current collector board

106‧‧‧Discharge anode collector board

108‧‧‧Charging negative current collector board

110a‧‧‧ positive end plate

110b‧‧‧Negative end plate

111a‧‧‧ front-end board

111b‧‧‧back-end board

112‧‧‧Electrolyte outlet

114a‧‧‧Positioning holes

114b‧‧‧Screw hole

116‧‧‧Electrolyte import

200, 200A‧‧‧discharge positive plate module

202‧‧‧Discharge positive plate

202a, 300a, 402a, 404a, 630a, 640a, 500a, 700a, 900a‧‧‧ positive

202b, 300b, 402b, 404b, 630b, 640b, 500b, 700b, 900b‧‧‧ back

204‧‧‧First through opening

206a, 206b‧‧‧ bulging

208‧‧‧first groove

210‧‧‧second groove

212‧‧‧Seal

214‧‧‧Discharge positive current collector board

216‧‧ ‧ partition

300‧‧‧Air electrode module

302‧‧‧Air electrode

304‧‧‧First barrier film

400, 400-1‧‧‧ front casing

400a‧‧‧ first side

400b‧‧‧ second side

402‧‧‧First electrolyte channel module

404‧‧‧Second electrolyte channel module

406‧‧‧ first opening

408, 413, 432, 436, 439, 608, 612, 634, 635, 636, 637, 644, 645, 647, 649a, 649b, 806 ‧ ‧ grooves

410, 415, 416, 417, 434, 437, 438, 508a, 610, 614, 631, 632, 633, 641, 642, 643, 646, 808 ‧ ‧ seals

412‧‧‧ second opening

414‧‧‧ third opening

418, 648‧‧ ‧ distribution of runners

420‧‧‧fourth opening

422‧‧‧ fifth opening

424‧‧‧ sixth opening

426‧‧‧First intermediate rectangular opening

428‧‧‧First electrolyte discharge manifold

430‧‧‧First electrolyte supply manifold

500, 500-1‧‧‧Charging positive plate module

501, 502‧‧‧ second through opening

503a, 503b‧‧‧ bulging

504‧‧‧Charging positive plate

505, 507‧‧‧ grooves

506‧‧‧Second isolation film

508‧‧‧Oxygen precipitation reaction catalyst

510‧‧‧Charging positive current collector board

600, 600-1‧‧‧ middle casing

602‧‧‧Second intermediate rectangular opening

604‧‧‧Second electrolyte discharge manifold

606‧‧‧Second electrolyte supply manifold

630‧‧‧ Third electrolyte channel module

630c‧‧‧ seventh opening

630d‧‧‧ eighth opening

630e‧‧‧ ninth opening

640‧‧‧4th electrolyte channel module

640c‧‧‧The tenth opening

640d‧‧‧ eleventh opening

640e‧‧‧Twelfth opening

700, 700A‧‧‧ negative plate

700c‧‧‧Intermediate rectangular opening

700d, 700e‧‧‧Flange

700-1‧‧‧Negative plate module

701‧‧‧Porous metal materials

702, 707‧‧‧Charged negative current collector board

703, 705‧‧‧ clips

704, 706‧‧‧Discharge anode collector board

800‧‧‧ rear housing

802‧‧‧ Third electrolyte discharge manifold

804‧‧‧ Third electrolyte supply manifold

900‧‧‧Charging electrode module

910‧‧‧Charging electrode

920‧‧‧ Third isolation membrane

G‧‧‧ Ambient air

1A is a perspective view showing an assembled structure of a metal air flow secondary battery in accordance with an embodiment of the present invention. Figure 1B is a rear perspective view of the structure of Figure 1A. 2A is a schematic perspective view of a metal air flow secondary battery in accordance with another embodiment of the present invention. 2B is an exploded view of the assembled structure of the front side of the metal air flow secondary battery according to FIG. 2A. 2C is an exploded view of the assembled structure of the back surface of the metal-air flow secondary battery of FIG. 2B. 3A is a schematic view showing a charging reaction working mechanism of the metal air flow secondary battery of FIG. 2B. 3B is a schematic view showing the discharge reaction working mechanism of the metal air flow secondary battery of FIG. 2B. 4A is a simplified diagram of the working mechanism of the charging reaction illustrated in FIG. 3A. 4B is a simplified diagram of the working mechanism of the discharge reaction illustrated in FIG. 3B. Figure 5 is a perspective view showing an assembled structure of a metal-liquid flow air secondary battery in accordance with another embodiment of the present invention. 6A is a schematic perspective view of a metal air flow secondary battery in accordance with another embodiment of the present invention. Fig. 6B is an exploded view showing the assembled structure of the front surface of the metal-air flow secondary battery according to Fig. 6A. Fig. 6C is an exploded view showing the assembled structure of the back surface of the metal-air flow secondary battery of Fig. 6B. Fig. 7A is a schematic view showing the charging reaction working mechanism of the metal-air flow secondary battery of Fig. 6B. Fig. 7B is a schematic view showing the discharge reaction working mechanism of the metal-air flow secondary battery of Fig. 6B. FIG. 8A is a simplified diagram of the working mechanism of the charging reaction illustrated in FIG. 7A. FIG. 8B is a simplified diagram of the working mechanism of the discharge reaction illustrated in FIG. 7B. Fig. 9 is a view showing the relationship between voltage and time of a metal air flow secondary battery according to another embodiment of the present invention.

Claims (22)

A metal air flow secondary battery comprising: a front housing formed by combining a first electrolyte passage module and a second electrolyte passage module, and having a first accommodating space for accommodating one An electrolyte plate; a discharge positive plate module, located on a first side of the front casing, comprising a discharge positive plate having a plurality of first through openings, wherein the first electrolyte channel module is interposed between the discharge positive plates Between the module and the second electrolyte channel module; an air electrode module between the discharge positive plate module and the front casing, comprising an oxygen reduction reaction catalyst, in contact with the electrolyte; a rear housing is disposed on a second side of the front housing; a negative plate is disposed between the rear housing and the front housing to be in contact with the electrolyte; and a charging positive plate module is located in the front housing Between the negative electrode plate, a charging positive electrode plate having a second through opening and an oxygen evolution reaction catalyst; and a middle casing located between the charging positive electrode plate module and the negative electrode plate, having a first The second space is accommodated to accommodate the electrolyte. The metal air flow secondary battery of claim 1, wherein the discharge positive electrode plate further comprises a plurality of protrusions disposed on a surface away from the air electrode module to form a plurality of air guides. The drainage channels are respectively connected to the first through openings. The metal air flow secondary battery according to claim 1, wherein the air electrode module includes an air electrode facing the discharge positive plate module; and a first isolation film disposed in the air The electrode and the front case are disposed, and the oxygen reduction reaction catalyst faces the first isolation film. The metal air flow secondary battery of claim 1, wherein the first electrolyte channel module comprises a first opening and a second opening and a third portion above and below the first opening The opening, the second electrolyte channel module of the front housing includes a fourth opening corresponding to the first opening, the second opening, and the third opening of the first electrolyte channel module a first opening and a sixth opening, the front housing further comprising: a first intermediate rectangular opening formed by the first opening and the fourth opening to form the first receiving space; a liquid supply manifold and a first electrolyte discharge manifold respectively adjacent to the first intermediate rectangular opening, wherein the first electrolyte supply manifold is constituted by the third opening and the sixth opening, and the first electrolysis The liquid discharge manifold is composed of the second opening and the fifth opening; and a plurality of distribution channels are located at the back of the first electrolyte channel module, communicating the first intermediate rectangular opening with the first electrolyte Supplying the manifold and connecting the first intermediate a rectangular opening and the first electrolyte discharge manifold to transport the electrolyte in the first electrolyte supply channel to the first accommodating space, and the electrolyte in the first accommodating space is The first electrolyte discharges the manifold output. The metal air flow secondary battery of claim 1, wherein the front housing further comprises a recess located in the first electrolyte channel module for accommodating the air electrode module and the discharge Positive plate module. The metal air flow secondary battery of claim 4, wherein the middle casing comprises: a second intermediate rectangular opening to form the second accommodating space; and a second electrolyte supply manifold And a second electrolyte discharge channel adjacent to the second intermediate rectangular opening; wherein the first electrolyte supply channel and the second electrolyte supply channel are corresponding and connected, the first The position of the electrolyte discharge manifold and the second electrolyte discharge manifold are corresponding and connected. The metal air flow secondary battery of claim 6, wherein the middle casing further comprises a groove surrounding the outer edge of the second intermediate rectangular opening and communicating with the second receiving space to accommodate The charging positive plate module. The metal air flow secondary battery of claim 4, wherein the rear casing comprises a third electrolyte discharge manifold and a third electrolyte supply manifold, the first electrolyte supply manifold Corresponding to and communicating with the position of the third electrolyte supply manifold, the first electrolyte discharge lane is corresponding to and communicates with the position of the third electrolyte discharge manifold. The metal air flow secondary battery of claim 1, wherein the charging positive electrode module further comprises a second isolation film disposed on a side of the charging positive plate away from the front casing. The metal air flow secondary battery of claim 1, wherein the rear case further comprises a recess for receiving the negative plate. A metal air flow secondary battery includes: a plurality of battery cells, wherein each of the battery cells includes a metal liquid secondary battery as described in claims 1 to 10, and two adjacent battery cells The rear housing of one is in contact with the other discharge positive plate module. A metal air flow secondary battery comprising: a front housing formed by combining a first electrolyte passage module and a second electrolyte passage module, and having a first accommodating space for accommodating one An electrolyte plate; a discharge positive plate module, located on a first side of the front casing, comprising a discharge positive plate having a plurality of first through openings, wherein the first electrolyte channel module is interposed between the discharge positive plates Between the module and the second electrolyte channel module; an air electrode module between the discharge positive plate module and the front casing, comprising an oxygen reduction reaction catalyst, in contact with the electrolyte; a middle casing, on a second side of the front casing, has a second accommodating space for accommodating the electrolyte; a negative plate module located at a first side of the middle casing and the front casing a third accommodating space for accommodating the deposition of the electrolyte and the generated metal; a charging positive plate module located on a second side of the middle casing, including a charging having a second through opening a positive electrode plate; and a charging electrode module located at the charging An oxygen precipitation reaction catalyst is in contact with the electrolyte between the electric positive plate module and the middle casing. The metal air flow secondary battery of claim 12, wherein the discharge positive electrode plate further comprises a plurality of protrusions disposed on a surface away from the air electrode module to form a plurality of air guides. The drainage channels are respectively connected to the first through openings. The metal air flow secondary battery of claim 12, wherein the air electrode module comprises: an air electrode facing the discharge positive plate module; and a first isolation film disposed in the air The electrode and the front case are disposed, and the oxygen reduction reaction catalyst faces the first isolation film. The metal air flow secondary battery of claim 12, wherein the first electrolyte channel module comprises a first opening and a second opening and a third opening above and below the first opening The second electrolyte channel module of the front housing includes a fourth opening, a fifth corresponding to the first opening, the second opening, and the third opening of the first electrolyte channel module An opening and a sixth opening, the front housing further comprising: a first intermediate rectangular opening formed by the first opening and the fourth opening to form the first receiving space; a first electrolyte a supply manifold and a first electrolyte discharge manifold respectively adjacent to the first intermediate rectangular opening, wherein the first electrolyte supply manifold is constituted by the third opening and the sixth opening, and the first electrolyte The discharge manifold is formed by the second opening and the fifth opening; and a plurality of distribution channels are located at the back of the first electrolyte channel module, communicating the first intermediate rectangular opening with the first electrolyte supply Associating and connecting the first intermediate Forming the opening and the first electrolyte discharge manifold to transport the electrolyte in the first electrolyte supply manifold to the first accommodating space, and the electrolyte in the first accommodating space is The first electrolyte discharges the manifold output. The metal air flow secondary battery of claim 12, wherein the front housing further comprises a recess located in the first electrolyte channel module for accommodating the air electrode module and the discharge Positive plate module. The metal air flow secondary battery of claim 15, wherein the middle casing comprises: a second intermediate rectangular opening to form the second accommodating space; and a second electrolyte supply manifold And a second electrolyte discharge channel adjacent to the second intermediate rectangular opening; wherein the first electrolyte supply channel and the second electrolyte supply channel are corresponding and connected, the first The position of the electrolyte discharge manifold and the second electrolyte discharge manifold are corresponding and connected. The metal air flow secondary battery according to claim 17, wherein the middle casing further comprises a groove surrounding the second intermediate rectangular opening and communicating with the second accommodating space to accommodate the Negative plate module. The metal air flow secondary battery of claim 12, wherein the discharge positive plate module further comprises a partition disposed on a side of the discharge positive plate away from the front case. The metal air flow secondary battery according to claim 12, wherein the negative electrode plate module comprises a porous metal material. The metal air flow secondary battery of claim 12, wherein the charging positive electrode plate further comprises a plurality of protrusions disposed on a surface away from the charging electrode module to form a plurality of oxygen guides. The drainage channels are respectively connected to the second through openings. The metal air flow secondary battery of claim 12, wherein the charging electrode module further comprises a charging electrode and a third isolating film, the charging electrode module has a charging positive electrode plate module The reverse electrode and a front surface opposite to the reverse surface are disposed on the opposite side of the charging electrode module, and the third isolation film is disposed on the front surface of the charging electrode module.